Reaction products of a polyethylene melamine and an alkyd resin



Patented Jan. 15, 1952 REACTION PRODUCTS A POLYETHYLENE MELAMINE AND ANALKYD RESIN Edward L. Kropa Old Greenwich, and Henry P.

Wohnsiedler, Darien, Conn., assignors to American Cyana-mid Company, NewYork, N. Y., a

corporation of Maine No Drawing.

7 1 This invention relates to the 1 production of newsynthetic'materials' and, more particularly, new resinous compositionswhich are ,especially suitable for use-in the plastics and coating arts.Still more particularly the invention is concerned with compositionscomprising the product of reaction ofingredients comprising (1) apolyethylene melamine (diethylene melamine or triethylene melamine) and(2) an alkyd resin containing unesterified hydroxyl groups. PreferablyApplication November 25, 1950, Serial No. 197,639

12 Claims; (Cl. 260-33.2)

It can beprepared, for instance, as described in the copendingapplication of Donald W. Kaiser and Frederic Schaefer, Serial No.165,861, filed June 2, 1950. The polyethylene melamines emthe alkydresin is one wherein. the. amount, of

polyhydric alcohol used inits preparation isat least 25% in excess ofthe theoreticalamount required for complete esteriflcation of thecarboxyl groups of the carboxylic component thereof. Thus, the alkydresin containing unesterified hydroxyl groups can be one obtained byreaction of ingredients comprising a polyhydric alcohol (6. g., di-,tri-, tetra-, pentaor hexahydric alcohol, or mixtures of any or all of.them)1,and a polycarboxylic acid (or vanhydride or po'lyanhydride), e.g., di-, tri-, tetrapentaor hexacarboxylic acid, or available anhydridesor polyanhydrides of such acids, or mixtures of any or, all of suchacids, anhydrides and polyanhydrides: In all cases, the polyhydricalcohol component is employed in substantial excess soas to. assure thatthe alkyd 'resin will contain unesterified hydroxyl groups Instead ofdiethylenemelamine or triethylene melamine alone; a mixture of thesespolyethylene melamines 'in any proportions can ari Jim/l Hg 1 N f H2Diethylene melamine can be represented by following general formula: IINHz ployed in practicing the present invention may be described as beings-triazine (1,3,5-triazine) derivatives wherein at least two of theamino nitrogen atoms of a polyamino-s-triazine each hasone ethylenegroup attached thereto instead of the two hydrogen atoms.

It is an object of the present invention to prepare a new class ofsynthetic materials, more particularly resinous compositions, which havev particular utility in the plastics and coating arts,

e. g., as coating, laminating, adhesive, impregnating, casting andmolding compositions as well as in other applications, for instance inthe treat ment of textiles, paper, etc. They also can be used ascomponents'of plastics and coating compositionsr Other objects of theinvention will be apparent to those skilled in the art as the description of the invention proceeds.

The present invention is based on our discovery that new and valuablematerials for use in coating, molding and other applications can beprepared by efiecting reaction between ingredients comprising (1)diethylene melamine and/or triethylene melamine and (2) an alkyd resinof the kind broadly described in the first paragraph of thisspecification and more specifically elsewhere herein. When theingredients are co-reacted only to a relatively low degree or extent,the resulting reaction products generally are soluble, but becomeinsoluble upon further advancement of polymerization, that is, becomesubstantially completely cured. The synthetic compositions of thisinvention, as initially prepared, are thermosetting in nature and can becured under heat in the form of films or moldings without the aid of acuring catalyst. The principal reaction which seems to take placebetween the polyethylene melamine and the alkyd resin containingunesterified hydroxyl groups appears to be one of addition. It alsoappears that the polyethylene melamines undergo self-polymerization, andthis latter type of reaction may compete wit the aforementioned additionreaction.

The alkyd resins which are used in practicing the present invention arethose which contain unesterified hydroxyl groups. From a practicalstandpoint it is desirable that a substantial average number ofunesterified hydroxyl groups be present in the resin molecule, and sucha result can be obtained, for example, by employing an amount ofpolyhydric alcohol in the preparation of the alkyd resin that is atleast in excess of the theoretical amount required for completeesterification of the carboxyl groups of the carboxylic component of thealkyd resin, e. g., or or or even 75 to 300% or more in excess of thetheoretical amount required. For instance, when the polyhydric alcoholused is pentaerythritol, the amount thereof which is ein- P ployed inmaking the alkyd resin advantageously is at least 50 in excess of thetheoretical amount required for complete esterification of "thecarboxylic ingredient used in preparing the alkyd resin. The generalmethod-of making such alkyd resins is that which is conventional in the'ar't.

Any polyhydric alcohol can be used in making the hydroxy-containingalkyd resins employed in practicing the present invention, and such analcohol can'contain other reactive or functional,

groups (in addition to -OI-I groupshas desired or as conditions mayrequire. Thus, polyhydric alcoholscan be employed that -con-tainreactive groups such as and other groups such as mentioned in ourc'open'ding application 'Serial No. 197,637, filed concurrentlyherewith, with particular reference to nitrogenouscompouads'usea as areactant With aa a polyethylene melamine in making a new class ofsynthetic materials; Examplesof such compounds are those derived from"glyceric acid,trihydroxy n-bu'tyric a'ci'd, 'trihydroxy isobutyricacid, etc., by reaction with'ammonia, ethanolamine, diethanolamine,et'c.';'al'so, compounds ob- More specific examples of polyhydricalcohols,

that'canbe used in preparing the hydroxy-con- I taining alkyd-resinreactant are:

Ethylene glycol 'Diethylene glycol Triethylene glycol Tetraethyleneglycol Hexamethylene-g-lycol Decamethylene glycol: Nonaethylene glycolPropylene glycol Dipropylene glycol Diethanolamine TriethanolamineMonoamide of glycer-ic acid N-hydroxyethyl glyceric acid amide Di(hydroxyethyl) melamine Tri- '(h-ydrokypropyl) melamineDi-(hydroxypropyl) ammeline Di-=(hydroxyethyl) ureaTrihydroxy-n-butyramide j Propenylene glycol 7 Butenylene glycolZ-ethyI-lB-hexanediol 1,3-buty1ene glycol Pentaeth'ylene glycolHeptaethylene glycol" Octaethylene glycol Decaethylene glycol 2butylgl,3'-cctanediol "(2- butyl 9 3 p'entyl :1I,-3-

' i a 1 "-75 such acids (ora mixture of such lactones), or a'propanediol) Erythi itol 2-ethyl-2-methylol-1-hexanol (2-ethyl-2-butyl1,3-propanediol) 6-methyl-2A-heptanediol (1-methyl-3-isobutyl-1,3-propanediol) Glycerol Pentaerythritol Dipentaerythritol t AdOnitOIXylitol Arabito'l Mannitol 'Dulc-itcl 'Sorb'itol V Polya'llyl alcohols(polymeric allyl alcohols), ;especially those which contain an averageof from 4 to 10 hydroxyl groups per molecule.

Etc.

More specific examples of polycarboxylic acids (or anhydrides thereofifaayailablelthat, can be employed :in producing the hydroxy-contain-ingalkyd-resin reactant are: crsatujrated aliphatic --p'olycarboxylic.acids, e. g., ;malonic, succinic, Q5 adipicyglutaric, pimelic, sebacic,azelaic, suberic,

tricarballylic, icitric, :etc,; unsaturated aliphatic polycarboxylic:acids, e. gt,:maleic,,- fumaric, Fit?- c'on'ic, citra'conic,monoha'lomaleic (-e. g., mono- 'chloromaleicl monohalofuma-ric -.('e.g.,, monochlcrofumaric), tmesacc'nic, la'conitic, acetylenedicarboxylic, ;etc.; cyclic polycarboxylic acids,

. more particularly nycloaliph'atic polycarboxylic The derivatives orproducts of 'the acids such as the 'cyclopentane-dicarboxylic acids,

' the alkyl :cycloalkane polycarboxylic acids, -etc.;

aromatic polycarboxylic' 'acids, -e.t-g., phthalic, :benzoyl :"phthalic,'terephthalic, 'benzophenone- 2;4'-dicarbox-ylic,-chlorinated phthalic--acid or anhydride (-e. gt, tetrachlorophthalic acid'or anhydrid'el,-etc.; as well as others that will be apparent :to :those :skilled :inthe art :f-rorn the toregoing illustrative :examples.

It is not essential that a single polyhydric-alcoh'ol or :9, :singlepolycarboxylic acid be used in making the v'hydroxy-con;tai'ning alkyd.resin, sincemixtures of polyhydric-alcohols in any proportions :(e..g., mixtures of two or more :of the aforementioned polyhydricalcohols}or (mixtures 0i polycarboxylic acids-,onof anhydrides :or,polyanhyilridesidfsuch acidsdfavailable, inany ;pro-

r aforem'entionedwpolycarboxylic acids) can be usedin making theialkydresinm Mixtures .of

'po'lyc'ai'ho:t-ylil': 'a'cids and of available .anhydrides and/ oravailable polyanhydridesgthereof in any *propor ti n's-alsocanibe'cmployed if *desired.

Iiikew'ise, it :is not "essential that the hydr'cxycontaining alkydresin be produced'byanirect kyd resin can be one'which has been modifiedby *incorporating-=therein-. a saturatedor unsaturated, normal orisomeric rmonohydric-alcohol, a saturated or unsaturated monocarboxylicacid or anhydride, or both such mono-esterifiable compounds, or amonohydroxy acid (or a mixture of such *acidslre. g., *v-hydroxyvalerieacid, p-hydroxypropionic :acid, -etcqfor a lactone of mixture of any orall of such monoesteriflable compounds. Examples of monohydric alcoholsthat can be used as modifiers of the alkyd-resin reactant are: propyl,isopropyl, butyl, 'isobutyl,

amyl, isoamyl, hexyl, octyl, decyl, dodecyl to tadecyl, inclusive,allyl, methallyl, l-chloroallyl, 2-chloroallyl, crotyl and cinnamylalcohols, 3-hydroxy-butene-1, 4-hydroxy-2-pentene, etc. The use ofmethyl and ethyl alcohols is not precluded, but in general thesealcohols are less suitable because of their lower boiling points. Asmonobasic acids can be employed, for example, saturated or unsaturated,normal or isomeric acids containing only one esterifiable group, e. g.,acetic, propionic to stearic, inclu-J sive, benzoie, etc., acids ofdrying, semi-drying and drying oils, e. g., the acids of tung oil,linseed oil, rapeseed oil, soyabean oil, castor oil, etc. Themonoesterifiable compound may be introduced into the esterificationprodu ct before during or after esteriiflcat ion of the polyhydricalcohol with the polybasic acid-under conditions such thatinteresterification of the monoesterifiable compound with theincompletely esterified polyhydric alcohol-polybasic acid reactionprodthey are soluble in all organic solvents, but that,

generally speaking, each is soluble in one or another organic solvent.In general, too, the alkyd resin which Weuse as a co-reactantwith apolyethylene melamine has a relatively low acid number, usually lessthan about 10 and, in many cases, less than 1, e. g., from zero orsubstantially zero to 0.9. I

The polyethylene melamine and hydroxy-containing alkyd resin areco-reactive (and, therefore, operative) in any and all proportions.Although the polyethylene melamine may constitute a relatively smallamount (8. g., from 0.5 to 3%) of the total weight of the polyethylenemelamine and alkyd-resin reactants, ordinarily it is desirable that thepolyethylene melamine constitute at least about 5% (or, in certaincases, a minimum of about or of the combined weight of polyethylenemelamine and alkyd resin. For certain applications of our new reactionproducts, it is sometimes desirable that the polyethylene melamineconstitute a major or preponderant proportion, by weight, of the mixturethereof with the alkyd resin, e. g., from 55 or 60% to 90 or 95% or moreby weight of the mixture. A preferred range of proportions for the usualapplications of our new reaction products is, by weight, from 5 to 75%of the polyethylene melamine to from to 95% of the hydroxy-containingalkyd resin. If the proportions are such that there is a theoreticalexcess of one reactant over the other, such excess remains in thereaction mass and may separately polymerize, forming a mixture with theprimary reaction product.

The temperature ofthe reaction also can. be

widely varied depending,- Ior instance, upon the particular reactantsemployed, the rapidity of reaction wanted, the particular propertiesdesired in the reaction product, and other factors. For example, thereaction temperature can be varied from a relatively low temperature ofthe order of or C..,up to and including the fusion or boilingtemperature of the reaction mixture if the reaction is carried out in'the absense of an active or inert liquid medium, or up to a d in l natheb po to h e ction mass if the reaction is effected while the primaryreactants are dissolved or suspended in such a liquidv medium.

The reaction can be effected in the absence of a solvent or otheradditive, or in the presence of (i. e intimately associated with) aninert solvent e. g., benzene, toluene, xylene, dioxanc, acetone, ethylmethyl ketone,;methyl isobutylke- ;tone, chlorobenzene, chloroform,ethyl-acetate,

carbon tetrachloride, methylene dichloride, ethylene dichloride, etc-.),or in the presence of an active liquid medium, that is, one which iscapable of entering into the reaction, more par- 'ticularly with thepolyethylene melamine reactant, for instance alcohols represented-by theformula ROH,.where R represents ,a ,monovalent'hydrocarbon radical, e.g., methyl, ethyl, propyl, benzyl, tolyl, phenyl, allyl and'others suchas are mentioned 'by way of illustration in our cop'endi'ng applicationSerial No. 197,638, filed concurrently herewith, where reference is madeto monohydric alcohols represented by the formula Rr-OH. Examples ofactive liquid media that can be used include methanol, ethanol,propanol, butanoLpentanol, hexanol, allyl alcohol, methallyl alcohol,benzyl alcohol and other monohydric acohols,rincluding those belongingto the saturated and unsaturated aliphatic and aromatic-substitutedaliphatic series; the various liquid alcohol-ethers, for example,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,etc.; as well as numerous others that will be apparentto thos skilled inthe art.

The inert or active liquid medium or additive, if employed, can be usedin any suitable amount Y ranginggfor instance,-from 0.1 to 40 M50 timesthat of the weight ofthe primary reactants. For examplefithe inert oractive liquid medium can be used in an amount such that the primaryreactants constitute from about 10% to about 30 or 35% by weight of thereaction mass. At the end oi the reaction period, the inert or unreactedliquid medium can be removed, if desired, from the reaction mass by anysuitable means, for instance by distillation, decantation, etc.; or thesolid reaction product can be separated from the liquid component of thereaction mass by filtration, centrifuging, etc.; or, in some cases, asfor instance in the preparation of a coating composition or a componentof such a composition, part or-all of the inert or, unreacted liquidmedium can be allowed to remain in the reaction mass, thereby to producea coating composition of a desired concentration of resin solids.

In order that those skilled in the art better may understand how thepresent invention can be carried into efiect, the following examples aregiven by way of illustration and not by way of limitation. All parts andpercentages areby mam r v APPTOX- spore-x. ;Pjar t,s T Molar Molar 1Ratio i "Rat o Glycerol;- 1,017 11' I2 gei caciah, 1,020 7 1 V r s 0 a,

are heated together; with stirring and with pro- 'vision for theremovalpf water, the temperature heingraised slowly to *225 C.'The'reactionmass is held at this temperature for approximately 3 hours,yielding an alkydjresin -containmg unes- -teri-fied jhydroxylgroups andhaving an acid numberof 4. This resin is an easily pou'rable liquid andis solublein a 1 1 mixture of ethyl alcohol and water It is usedas a co--reactant The triethylene melamine is dissolved in the solvent; afterwhich the alkyd resin is added th re o 'ZIh r su t n vvmixture is heatedwith stirring underreflux at boiingtemperature for from 1 to hours,yield a s lut o containin the triethylener melamine- -alkyd'resin.reaction product. Thissglutioneis filtered to remove any insoluble"matter. Elesible films are obtained by areheatfed together, withproyis'ion-made forthe discharge of water resulting from thecondensation reaction; to a "temperature on-2T5 -C., and

the reaction is then allowed-to proceed at 215- 225 C. 'for a total pf:4 hours; A yery viscous resin containing =unesterified hydrgxy-lgroups'and :having an acid number of '9 is obtained. This resin 'issoluble in ethyl alcohol and in a 1-1 mixture of water and ethylalcohol; and can'be thinned 'witl water g-to the extent of flog-ramsthereof per 1 00 grams of resin. It is coreacted with triethylenemelamine as -descri=bed below:

The same procedure is followed as described under Example *2. As in--that-example, so too in this example the -triethylene melamine-reactspartly with the ethyl alcohol and partly with baking panels coated withthecfiltered solution for from2 to 3 hours at 1202 150 (3. V

s 3 V t r A Approx. 7 Pants Molar 1 Ratio Ethylene glycol 124 2 Sebacicacid 202 1 -;A Z mixture of :the above, ingredients is ql'ieated withstirring, *under conditions allowing -;f.0r the gdischargeof water,-ata;,sl ow1y rising tempera ture oyer aperiodiof 3 hours to 225 .C.Thereaction mass; is-thenheld at this temperature ior about .7' hoursorder to complete the reaction. The ,resllltingsalkydresin containsunesterified hydroxyl groups and has an acid number of about f is a s t,waxmateria with n softening point of -'65 C. r V e r 7 1:1 volumemixture of acetone and ethyl-althe resulting reaction product portionsthereof arefiowed upon glass and-metal-panels. The ex-.

:cess is allowed .to drain :off at room temperature,

after :whichxthe panels are baked for about 3 ore-incurs at: about 130C.FlexibleJtough films havingeoodsorfiaceanrotective characteristics areformed on the panels.

the alkyd resin throughtheir-respective hydroxy groups. Baked filmsproduced-by heating panels coated with the liquid reaction product aresomewhatjharder -than-films obtained bysi-milarly baking the product of-Examp1e'2, and form good surface-protective coatings on thepanel's'nxAMPLE .4

' hydride'in the ratio of 7i5imoles propylene glycol,

womm tiens .efiinsmfien fimmwedn-s h S and V i moles'f urnaric acidand*2 moles phthalic anhydriole, these ingredients being heated together atabout .85-95 C. under anhydrous reflex conditions until anorganicQsolvent-soluble alkyd resin'havin' an acid number of about '10is obtained. 1A productsimilarto'that of Example 1 is obta d j VVIEXA'MPLEG Approx.

' Parts ,Molar -Ratio tGlydero'l 291 L58 Sebacie-acid 09;.; 404 1.0

forzthe discharge-of waten r 3 /2 ho s at a icemprerature 'rane ns irom;2. 0 1G- t 30? Ct the eb rri dineaye y visc us -,1 qu d -resincontamn inesterifiedi hrd qxyl eroups and havin an acid number of 4. Becauseof the ratiosof' the other examples herein, the reaction mixture can beheated freely without danger of gelation during the reaction period.This resin is used as a coreactant with diethylene melamine in themanner described below:

' Parts Alkyd resin of A--. 25 Diethylene melamine '75 Ethylene glycolmonoethyl ether 200 The same procedure is followed as describedv underExample 2 with the exception that the mixture of reactants is heated foronly about 1 to 1 hours at about 130140 C. When portions of theresulting solution are cast to form films, hard films are obtained afterheating for 3 hours at 65 C. and then for 1 hours at 150 C.

EXAMPLE 7 Same as in Example 6 with the exception that 50 parts each oftriethylene melamine and of the same alkyd resin employed in Example 6are used in place of 75 parts of triethylene melamine and 25 parts ofalkyd resin. Similar results are obtained.

EXAMPLE 8 In this example the alkyd resin containing unesterifledhydroxyl groups is prepared by a transesteriflcation reaction.

Approx. Parts Molar Ratio Pentaerythritol 735 3 Dibutyl sebacate l, 1802 All of the pentaerythritol and 150 parts of the dibutyl sebacate areheated together with stirring in a reaction vessel which is connected toa waterco'oled condenser for condensing the butyl alcohol formed as aby-product of the reaction. After heating for about 65 minutes at about226-228 0., a clear solution results. The remainder of the dibutylsebacate is now slowly added over a: period of about 3% hours whilecontinuing to heat the reaction mass at about 226-241 C.

After heating for an additional 10 minutes, vacuum is applied for about20 minutes. amount of butyl alcoholcollected is about 96% of thetheoretical. The productis a light-colored, soft, plastic materialhaving an acid number of 0.11.

Approx. Parts Molar Ratio Alkyd resin of A 205 0. 375 Triethylenemelamine --1'50 1. Ethylene glycol monomethyl ethcr 060 A reactionvessel provided with a reflux condenser and containing a mixture of theabove ingredients is placed in a heated oil bath,-the mixture beingbrought to reflux temperature in 15 minutes. Heating under reflux iscontinued for 45 minutes, the temperature of the reaction mass beingabout 125 C. at the end of the reflux period. The solution contains aconsiderable amount of'fiocculent, insoluble reaction product.

The total A sample of the solution comprising a reaction product of theaforementioned ingredients is airdried on a glass plate, yielding an"elastomeric, translucent film.

The flocculent reaction product is separated from the solution anddried. Samples of the dried material yield soft, elastic articles whenmolded at about 155 C. under a pressure of about 4000 pounds per squareinch.

Examples 9 and 10 illustrate the use of an alcohol-reaction product of apolyethylenemelamine, specifically a methanol-reaction product oftriethylene melamine, as a means of introducing a polyethylene melamineinto an alkyd resin which initially contains unesterified hydroxylgroups.

EXAMPLE 9 PREPARATION OF A REACTION PRODUCT OF TRI- ETHYLENE MELAMINEAND METHYL ALCOHOL Parts Triethylene melamine '60 Methyl alcohol 180 areheated together under reflux at the boiling temperature of the mass for2 hours and 40 minutes, after which the solution of the reaction productis pressure-filtered to remove insoluble material that is present. Whena sample of this solution is air-dried it yields a clear, resinous film.The solution is used as a co-reactant with a hydroxy-containing alkydresin as described under 0.

PREPARATION OF ALKYD RESIN Approx. Parts Molar Ratio Propylene glycol(propanediol-1,2) 50.7 2 Fumaric acid 38.7 1

An alkyd resin containing unesterified hydroxyl groups is prepared byheating a mixture of the above ingredients for 3% hours at.140- 192 C.,the mixture being brought to a temperature of C. in 30 minutes and to ahigher temperature of the order of 180190 C. in another hour. At the endof' the reaction period the cool alkyd resin is a somewhat stiff,translucent; plastic material.

PREPARATION OF REACTION PRODUCT OF A. AND B EXAMPLE 10 Same as in A ofExample 9.

T An alkyd resin containingfunesterified hydroxyl groups is prepared byheating a mixture of the above ingredients under reflux forapproximately 2' ioursamhe boiling temperature or the mass. Theresulting resin is used as a reactant with the triethylenemelamine-methanol reaction product of A as described below:

Parts Triethylen'e 'rneiamine methanol i'e'actioi'l .product of A 60Alkyd resin of B 40 Triethylne' melamine methanol reaction I plffiallcllOf A Of B V Tiie c ear solutions that resmt from mixing the aboveirigredints in the specified proportions are flowed on glass plates,air-dried for about l6 bears and then baked for about 4 ours at 195 c..The film of (a5 is hard, almost water-white in color and is barelyscratchable at the end of this baking period. When it is baked for anadditional hour at lfillf Ci, the film is further hardened and ispractically unaffected when immersed in water at room; temperature for 2hours. The film of (b) is somwhat'tacky at the end of the 4-hour bakingperiod at 105 C. but can be hardened by furthei heating at 150 0, whenthe alkyd resin or B alone is similarly baked a panel, the baked iilrnissoft and very tacky. V 7

It will be understood, of course, by those skilled in the art that ourinvention is not limited to the" specific reactants, proportions thereofand conditions of reaction given by way of illustratioii iri theforegoing examples. For instance,- in any of the examples whereindiethylerle' mien-'- mine' has been used, we can employ an equivalentamount of triethylene melaminei also, in any of the examples whereintriethyleiie melamine has been utilized, we can use an equivalent amountof diethylene melamine; furthermore, in any of the examples wherein asingle polyethylene melamine has'been used, we can employ in lieuthereof a mixture of diethylene melamine and trithylene melamine in anyproportions, as will reticalamount required for complete esteriiicationof the carboxyl groups of the carb'oxylic cam: ponent of thealkydres-in:

Glycerine and succinic acid Triethylene glycol and sebacic acidPentaerythritol and adipic acid assay/arl fifametlfiylene 'g1yc6i andphthalic anhydride Penta'erythritol, butyl alcoholand azelaicacidGlycerine; linseedoil, fatty acids and phthalic anhydride v V Glycerinc,diethylene glycol, sebaci'c acid and phthalic anhydride Ethylene glycoland maleic anhydride Glycerine and maleicanhydride Diethylene glycol,maleic anhydride and phthalic anhydride Diethylene glycol and itaconicacid H Ethylene glycol, maleic anhydride and succinic acid Ethyleneglycol; itaconic acid and phthalic anhydride methylene glycol, maleicanhydride and tuiig oil acids Ethylene gl'y'col, maleic anhydr'ide,linseed oil acids and phthalic .anhydride Diethylene glycol and-maleicanhydride Ethylene glycol, maleic anhydride and stearic acid Diethyleneglycol, maleic anhydride and decyl alcohol I q Ethylene glycol,-maleic-'anhydride, octyl alcohol and acetic anhydride" Diethyleneglycol, fumaric acid, tetrahydroabietyl alcohol and linseed oil fattyacids Alpha-propylene glycol and maleic anhydride Dietliylene glycol,fiimaric acid and benzyl alcohol Diethylene glycol, fumaric acid andtetrahydroabietyl alcohol Ethylene glycol, fumaric acid and omega-hydroxy'decanoic acid 7 Fumaric acid,- diethylene glycol and linseed oilfatty acid monoglycerides Etc.

Illustrative examples of ingredients that'can be used in'a similarpreparation of other hydroxycontaining alkyd resins are given, forexample, in Kropa Patent No. 2,510,503, for instance in columnlS, lines2 6 -36'. Mixture of different hydroxy-containing alkyd resins in anyproportions can be used if desired.

The reaction between the polyethylene mel- In these formulas R and R.each represents a monovalent hydrocarbon radical, R represents a memberof the class consisting of divalejrit aliphatic hydrocarbon radicals anddivalefit aromatic-substituted aliphatic hydrocarbon radicals, and 'nrepresents any positive integer, e. g.,1, 2, 3, 4, 5, 10, 20, 50, or anyhigher num-- ber', thel-imit on the value of n being governed only" bythe type of product wanted and the availability of the alcohol-ethrsrepresented by the forinu-IaflMixtures of monohydric alcoholsrepresented by the aforementioned formulas can be used if desired. Thehydroxy group in the compounds represented by the above formulas can beattached to a primary, secondary or tertiary carbon atom. V

illustrative examples of radicals represented by R in the formula R-'OHand R in the formula R& (OR.")'1LOH are: monovalent aliphatic hy- 4 withreference to R and R.

1'3" drocarbon radicals, e. g., methyl, ethyl, propyl, isopropyl,n-butyl, sec.'-butyl, tert.'-butyl, n-amyl, isoamyl, tert.-amyl, hexyl,heptyl, octyl, nonyl, decyl to octadecyl, inclusive, allyl, methallyl,ethallyl, crotyl, butenyl, is'obutenyl, 2-butenyl, butynyl, oleyl,linalyl, etc., including cycloaliphatic, e. g., cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.; monovalentaromatic-substituted aliphatic hydrocarbon radicals, e. g., benzyl,cinnamyl, phenylethyl, phenylpropyl, phenylallyl andotheraryl-substituted aliphatic hydrocarbon radicals corresponding tothe examples of the monovalent unsubstituted aliphatic hydrocarbonradicals just mentioned; monovalent aromatic hydrocarbon radicals, e.g.,

phenyl, diphenyl or xenyl, naphthyl, etc.; and

monovalent aliphatic-substitutedaromatic hydrocarbon radicals, e. g.,tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl,etc. In'brief, Rand R each represents any hydro carbon radical includingthejlower alkyl radicals, e. g., methyl, ethyl, propyl, butyl, etc.

' Illustrative examples of divalent radicals rep resented by R." in theaboveformulafor an alcohol-ether are: divalent aliphatic hydrocarbonradicals and divalent aromatic-substituted aliphatic hydrocarbonradicals corresponding to the examples of monovalent aliphatichydrocarbon radicals and monovalent aromatic-substituted aliphatichydrocarbon radicals mentioned above Thus, R". can represent divalentradicals such, for instance, as divalent aliphatic hydrocarbon radicals,e. g., ethylene, propylene (trimethylene), propenylene, butylene,isobutylene, pentylene, isopentylene, butenylene, hexYlQne, heptylene,octylene, nonyle'ne,"decylene to octadecylene, inclusive, includingdivalent cycloaliphatic hydrocarbon radicals, e. g., cyclopentylene,cyclohexylene, cyclohexenylene, cycloheptylene, etc.; and divalentaror'natic-substituted aliphatic hydrocarbon radicals, e. g.,phenylethylene, phenylpropylene, naphthylisobutylene, xylylene, etc. f

More specific examples of hydroxy compounds that can be used as media inwhich the reaction between the primary or main reactants is effected,and whereby modification of the fundamental reaction product is secured,are listedbelow:

Methyl alcohol Pentanol-2 Hexanol-3 PhenylmethylcarbinolDiisopropylcarbinol Lauryl alcohol Cyclobutanol MethylcyclobutanolCyclohexanol Ethylene glycol monobutyl ether Diethylene glycol monoethylether Propylene glycol monophenyl ether actant such as an amine,e.{g.-,- n butylamine,

when the reaction between the polyethylene;mel-- amine and the hydroxycompounddoesnotpror' ceed-as rapidly as is desired. Other aminesias wellas other nitrogenous compounds) that can be used'for this purpose aregivenin our co.-

pendingapplication Serial No. 197,637). Such nitrogenous compounds(amines, amides, etc) by introducing other modifying bodies before,

during or after effecting reaction between the primary components. Forinstance, we canincorporate into the fundamental reaction products,during their preparation or after they have been formed, such modifiersas melamine-aldehyde condensation products (e. g., melamineformaldehydecondensation products), urea-aldehyde condensation products (e. g.,urea-formaldehyde condensation products), urea-melamine-aldehydecondensation products (e. g., urea-melamine-formaldehyde condensationproducts), protein-aldehyde condensation products,

aminodiazine-aldehyde condensation products, aminotriazole-aldehydecondensation products, aniline-aldehydecondensation products,phenolaldehyde condensation products (e. g., phenoliormaldehydecondensation products), furfural condensation products, ester gums,water-soluble cellulose derivatives, natural gumsand resins such asshellac, rosin, etc., polyvinyl compounds such as polyvinyl alcohol,polyvinyl esters (e. g., polyvinyl acetate, polyvinyl butyrate, etc.),polyvinyl ethers, including polyvinyl-acetals, e. g.,

taining, for instance, from 15 to 95 parts by weight of a thermosettingor potentially thermosetting resin of thekind with which this inventionis concerned and from to 5 parts of a fatty oil or fatty o-ilacid-modified alkyd resin, numerous examples of which are given, for example inMoore Patent No. 2,218,474, .issuedOctober15,.1940. i i l YDyes, pigments, driers, curing agents. (insome cases where a moreaccelerated cure is desired), plasticizers, mold lubricants, opacifiersand various fillers (e. g"., wood flour, glass fibers, asbestos, mineralwool, mica dust, powdered quartz, titanium dioxide, zinc oxide, talc,China clay, carbon black, etc.) may be compounded by conventionalpractice with the synthetic materials of our invention, as desired or asconditions may require, in order to provide a coating, molding or othercomposition best adapted to meet a particular service use.For'additional and more detailed information concerning the modifyingingredients that may be "employed in producingcoatingcomposition'sjfromour new resins, reference is made;

to the aforementioned Moore patent.

' The modified and unmodified reaction prod-' The solubleresins of thisinvention also canbe" dissolved in appropriate solvents. 'Some of thesolvents that may be employed to dissolve a particular reaction productof our'invention include benzene, toluene, xylene, amyl acetate,butanol, methyl ethyl ketone, etc. can be used as laminating'varnishesin the production .of laminated articles wherein sheet materials, e. g.,paper, cloth, sheetasbestos, etc., are coated or coated andimpregnated'with the resin solution, superimposed and thereafter unitedunder heat and pressure. They also can be employed as an adhesive inmaking laminated plywood, as an impregnant' of pulp preforms from whichmolded articles thereafter are made by subjectin the impregnated preformto heat and pressure, as impregnants for electrical coils and for otherelectrically insulating applications, for bonding together abrasivegrains in the production of resin-bonded abrasive articles such, forinstance, as grindstones, sand papers, etc., in the manufacture ofelectrical resistors,"etc. They' also can be used for treating textilematerials (e.g., cotton, linen, rayon and other cellulosecontainingtextiles, 'wool, silk and other natural or synthetic proteinaceous'materials, including 1. A composition comprising the product ofreaction of ingredients comprising (l) a polyethylene melamine which isa polyamino-s-triazine wherein at least two of the amino nitro-" genatoms each has one ethylene group attached thereto instead of the twohydrogen atoms and (2) an alkyd resin containing unesterified hydroxylgroups, the amount of polyhydric alcohol used in the preparation of saidalkyd resin. being at least 25% in excess of the theoretical amountrequired for complete esterification of the carboxyl groups of thecarboxylic component of the said alkyd resin.

2. A composition. as in claim 1 wherein the polyethylene melamine of (l)is diethylene mel-' amine, the formula for which is mo' N N on, at aN v3. A composition asin claim 1 wherein the The dissolved resins amazesl'6polyethylene melamine of; (I) is triethylene mel amine, the formulafor.which is im-eon.

H1O N CH2 Peri (Ln l H: N H2 4. A composition comprising the product ofreaction. of ingredients comprising (1) a polyethylene. melamine whichis a polyamino-s-triazine wherein at leasttwo of the amino IlitI'O-x genatoms each has one ethylene group attached thereto instead of the twohydrogen atoms and (2) an alkyd resin containing unesterified hydroxylgroups and which is obtained by reaction of ingredients. comprising adihydric alcoholand a polycarboxylic acid, the amount'of dihydricalcohol being at least 25% in excess of the theoretical amount requiredfor complete esterification of all the carboxyl groups of thepolycarboxylic acid. a

5. A composition comprising the product of reaction of ingredientscomprising (1) a poly-' ethylene melamine which is apolyamino-s-triazine wherein at least two of the amino nitrogen atomseach has one ethylene group attached thereto insteadv of the twohydrogen atoms and (2) an alkyd resin containing unesterified. hydroxylgroups and which is obtained by reaction of ingredients comprising atrihydricv alcohol and a polycarboxylic acid, vthe amount oftrihydricalcohol being at least 25% in excess of the theoretical amount.required for complete esterification of all the carboxyl groups of thepolycarboxylicacid.

6. A composition comprising the productv of reaction of ingredientscomprising (1) a polyethylene melamin'e which is a polyamino-s-triazinewherein at least two of the amino nitrogen atoms each has one ethylenegroup attached thereto instead of the two hydrogen atoms and (2) analkyd resin containing unesterified hydroxyl groups, the 'polyhydric.alcohol component of the said' alkyd resin being pentaerythritol and theamount of pentaerythritol used in the preparation of said alkyd resinbeing, at least 50% in excess of the theoretical amount required forcomplete esterification of the carboxyl groups of the carboxyliccomponent of the said alkyd resin.

7. A composition comprising the product of reaction of (l) triethylenemelamine, the formula for which is Hsq s CH2 mc 'N N )CH:

wherein at least two of the amino nitrogen atoms eachhas one ethylenegroup attached thereto instead of the two hydrogen atoms and (2) analkyd resin containing unesterified hydroxyl groups, the amount ofpolyhydric alcohol used in the preparation of said alkyd resin being atleast 25% in excess of the theoretical amount required for completeesterification of the carboxyl groups of the carboxylic component of thesaid alkyd resin.

9. A method as in claim 8 wherein the reaction between the ingredientsof (1) and (2) is efiected in the presence of a monohydric alcohol.

10. A method as in claim 8 wherein the reaction between the ingredientsof (1) and (2) is efiected in the presence of an alcohol-etherrepresented by the formula R'--(OR")1r-OH where R represents amonovalent hydrocarbon radical. R" represents a member of the classconsisting of divalent aliphatic hydrocarbon radicals and divalentaromatic-substituted aliphatic hydrocarbon radicals, and n represents apositive integer.

11. A method as in claim 10 wherein the al- 18 cohol-ether is ethyleneglycol monomethyl ether.

12. A method as in claim 8 wherein the reaction is effected by heating aliquid medium containing the ingredients of (1) and (2) and in which thesaid ingredients are inert, said reaction being efiected at atemperature not exceeding the boiling temperature of the reaction mass.

EDWARD L. KROPA.

HENRY P. WOHNSIEDLER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date Dudley Oct. 3, 1950 OTHER REFERENCESNumber

1. A COMPOSITION COMPRISING THE PRODUCT OF REACTION OF INGREDIENTSCOMPRISING (1) A POLYETHYLENE MELAMINE WHICH IS A POLYAMINO-S-TRIAZINEWHEREIN AT LEAST TWO OF THE AMINO NITROGEN ATOMS EACH HAS ONE ETHYLENEGROUP ATTACHED THERETO INSTEAD OF THE TWO HYDROGEN ATOMS AND (2) ANALKYD RESIN CONTAINING UNESTERIFIED HYDROXYL GROUPS, THE AMOUNT OFPOLYHYDRIC ALCOHOL USED IN THE PREPARATION OF SAID ALKYD RESIN BEING ATLEAST 25% IN EXCESS OF THE THEORETICAL AMOUNT REQUIRED FOR COMPLETEESTERIFICATION OF THE CARBOXYL GROUPS OF THE CARBOXYLIC COMPONENT OF THESAID ALKYD RESIN.